Mono(alkyl and alkenyl)mono-omega-alkynylaralkyl phosphonates

ABSTRACT

MONO (ALKYL AND ALKENYL) MONO-W-ALKYNYL ARYL-AND ARALKYPHOSPHONATES ARE DESCRIBED. THE COMPOUNDS ARE COMBINED WITH ESTERS OF CERTAIN CYCLOPROPANECARBOXYLIC ACIDS, E.G. PYRETHRINS, ALLETHRIN AND RELATED COMPOUNDS TO FORM SYNERGISTIC INSECTICIDAL COMPOSITIONS.

United States Patent O 3,652,741 MON(ALKYL AND ALKENYL)MONO-OMEGA-ALKYNYLARALKYL PHOSPHONATES Ronald Eugene Montgomery, Middleport, andHarry Hobart Incho, Medina, N.Y., assignors to FMC Corporation, NewYork, N.Y.

No Drawing. Continuation-impart of application Ser. No. 630,204, Apr.12, 1967, which is a continuation-in-part of applications Ser. No.559,422, June 22, 1966, and Ser. No. 624,689, Mar. 21, 1967. Thisapplication Feb. 18, 1969, Ser. No. 800,264

Int. Cl. A01n 936; C07]? 9/40 US. Cl. 260-956 3 Claims ABSTRACT OF THEDISCLOSURE Mono (alkyl and alkenyl) mono-w-alkynyl aryl-andaralkylphosphonates are described. The compounds are combined withesters of certain cyclopropanecarboxylic acids, e.g. pyrethrins,allethrin and related compounds to form synergistic insecticidalcompositions.

CROSS REFERENCE TO RELATED APPLICATIONS This application is acontinuation-in-part of Ser. No. 630,204, filed Apr. 12, 1967 nowabandoned, which is a continuation-in-part of Ser. No. 559,422, filedJune 22, 1966 and Ser. No. 624,689 filed Mar. 21, 1967, both nowabandoned; and is related to co-pending applications Ser. No. 559,745,filed June 23, 1966, now US. Pat. 3,555,123, and Ser. No. 634,121, filedApr. 27, 1967 now US. Pat. 3,557,259, which are continuations-in-part ofSer. No. 540,175 filed Apr. 5, 1966, and Ser. No 559,412 filed June 22,1966, respectively, both now abandoned.

BACKGROUND OF THE INVENTION Among the most widely used insecticidestoday are the pyrethrins, the active principle of pyrethrum flowers(Chrysanthemum cinerariaefolium), which have a high order ofinsecticidal activity and a low mammalian toxicity. The relatively highcost and the uncertain supply of pyrethrins have encouraged attempts toprepare synthetic insecticides which retain the desirable properties ofpyrethrins. It has long been known that synthetic products having abasic structural similarity to pyrethrins in that they are esters ofcertain substituted cyclopropanecarboxylic acids, in particular2,2-dimethyl-3-(2-methylpropenyl)cyclopropanecarboxylic acid (which isalso known as chrysanthemumic acid and will be so referred to herein),exhibit insecticidal activity of a significant order.

The wide market which pyrethrins and related synthetic insecticidesenjoy today is due primarily to the discovery of certain additives whichenhance the activity of these insecticides. These additives, commonlycalled synergists, are agents which may or may not themselves exhibitinsecticidal activity, but which when combined with pyrethrins orrelated compounds, produce new insecticides, having an effectivenesssignificantly greater than the sum of the effectiveness of thecomponents when used separately. A great deal of time and eflort hasbeen devoted to the search for efiective synergists. One of the mosteffective and most widely used of the pyrethrins synergists is thecompound piperonyl butoxide, which is described in synergisticcombination with pyrethrins in Wachs US. Pat. 2,550,737. Unfortunately,it has been found that many compounds which are excellent synergists forpyrethrins are not nearly as effective when used with allethrin or othersynthetic cyclopropanecarboxylic acid esters.

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SUMMARY OF THE INVENTION This invention relates to novel compositionsfor the control of insects and acarids and in particular to suchpesticidal compositions containing pyrethrins, allethrin, or relatedinsecticidal cyclopropane carboxylic acid esters, in combination withcertain mono(alkyl or alkenyl) monow-alkynyl aryland aralkylphosphonatesas synergists for insecticidal activity.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The synergistic phosphonates ofthis class have the structural formula:

OR CECH wherein R is an alkyl, alkenyl, or alkoxyalkyl group of from oneto about twenty carbon atoms, straight or branched chain; R is analkylene group of one to six carbon atoms, straight or branched chain; Ris hydrogen or methyl; n is an integer from 0 to 3 inclusive; Ar is anaromatic radical such as phenyl, pyridyl, thienyl, pyrryl, furanyl,isothiazyl, and the corresponding benzo-derivatives; Y is halogen; m isan integer from 0 to 2 inclusive; and X is oxygen or sulfur. When n is 2or 3, the R groups may be the same or diiferent. Similarly, when m is 2,the Y groups may be the same or different.

Particularly preferred are these compounds represented by the followingformulae:

OR2CECH ORzCECH and wherein the radical R, can be any of the very largenumber of radicals which have been found to form insecticidalchrysanthemumates. For example, this class of esters includes thepyrethrins, allethrin (3-allyl-2-methyl- 4-oxo-2-cyclopentenylchrysanthemumate) and related insecticides as described by Schechter andLa Forge in US. Pat. 2,661,374; cyclethrin (3-(2-cyclopentenyl)-2-methyl-4-oxo-2-cyclopentenyl chrysanthemumate) as described by Guest andStansbury in US. Pat. 2,891,888; furethrin (3-furfuryl-2-methyl 4oxo-2-cyclopentenyl chrysanthemumate) as described in NationalDistillers Products, British Pat. 678,230; barthrin (6-chloropiperonylchrysanthemumate) and its bromo analog, as described by Barthel et al.in US. Pat. 2,886,485; dimethrin (2,4-dimethylbenzyl chrysanthemumate)and the 3,4-dimethyl isomer, as described by Barthel in US. Pat. 2,857,-309; compounds of the class of (cyclohexene-1,2-dicarboximido)methylchrysanthemumates as described in Belgian Pat. 646,399 and(cyclohexadiene-1,2-dicarboximieio)methyl chrysanthemumates as describedin Belgian Pat. 651,737, both to the Sumitomo Chemical Company, Ltd.;and related compounds such as phthalimidoalkyl and substitutedphthalimidoalkyl chrysanthemumates as described in Sumitomo Belgian Pat.635,902. Other insecticidal esters of chrysanthemumic acid also formsynergistic combinations with the phosphonates of this invention.

Synthetic esters of other cyclopropanecarboxylic acids, closely relatedto chrysanthemumic acid, but having some variation in the substituentson the cyclopropane ring, have also been found to have insecticidalactivity. Esters of this class are described in Netherlands application6711587 to Sumitomo Chemical Company, Ltd. and in Belgian Pat. 690,984to National Research Development Corporation. The useful insecticides ofthis class, which form synergistic combinations with the phosphonates ofthis invention, include esters of2,2,3,3-tetramethylcyclopropanecarboxylic acid, particularly(-benzyl-3-furyl) methyl 2,2,3,3-tetramethylcyclopropanecarboxylate.

The preparation of the phosphonates of this invention and theirsynergistic insecticidal properties are illustrated in the followingexamples, which are not intended to be limitative of the variety ofprocedures which are applicable to the synthesis of mono(alkyl oralkenyl) mono-walkynyl phosphonates, or of the many insecticidalcombinations in which they are effective. In these examples, alltemperatures are in degrees centigrade.

EXAMPLE 1 Preparation of butyl 3-butynyl phenylphosphonate The startingmaterial, butyl phenylphosphonochloridate, was prepared fromdichlorophenylphosphine as follows: To a cold, stirred solution of 30.0g. of butanol and 41.4 g. of triethylamine in about 300 ml. of ethylether was added dropwise a solution of 34.6 g. ofdichlorophenylphosphine in about 200 ml. of ethyl ether while thetemperature was maintained below 0 When addi tion was completed, themixture was allowed to warm to room temperature. Stirring was continuedovernight. The mixture was filtered, and the filtrate was concentratedunder reduced pressure. The residual oil was distilled under reducedpressure to give 39.5 g. of dibutyl phenylphosphonite, B.P. 120131/ ca.1.0 mm. Chlorine gas was bubbled into 38.5 g. of dibutylphenylphosphonite for about three hours. The mixture was warmed to 50under aspirator vacuum to remove butyl chloride. The residual colorlessoil was dissolved in 100 ml. of benzene, washed with 1% sodium hydroxideand with water, dried over magnesium sulfate, and the dried solutionconcentrated under reduced pressure to give 30.6 g. of pale yellow butylphenylphosphonochloridate.

A solution of 15.6 g. of butyl phenylphosphonochloridate in 15 ml. ofbenzene was added dropwise with stirring to a cold solution of 5.2 g. of3-butyn-1-ol and 7.5 g. of triethylamine in 45 ml. of benzene While thetemperature of the mixture was kept below When addition was complete,the mixture was slowly warmed to approximately 50 at which temperatureit was stirred for one hour, then allowed to stand overnight at roomtemperature. The mixture was filtered, and the filtrate was washed withdilute hydrochloric acid, dilute sodium hydroxide, and water. The washedfiltrate was dried over magnesium sulfate and concentrated under reducedpressure. The residue was distilled under reduced pressure to give 10.1g. of colorless butyl 3-butynyl phenylphosphonate. The stem and bathtemperatures were 9l-106 and 130-141 respectively with the pressure at 2microns.

Analysis.Calcd for C H O P (percent): C, 61.41; H, 7.53. Found(percent): C, 61.61; H, 7.55.

4 EXAMPLE 2 The synergistic activity of butyl 3-butynylphenylphosphonate The synergistic insecticidal activity of butyl3-butynyl phenylphosphonate in combination with representativeinsecticidal cyclopropanecarboxylates, e.g. chrysanthemumates, wasdetermined by the following procedure: The test compound and thecyclopropanecarboxylate were dissolved in 70 parts by volume of acetone,which was then made up to parts by volume by addition of water. A groupof 30 to 40 houseflies (Musca domestica L.), immobilized under carbondioxide, was placed on a moist filter paper on a Buchner funnel attachedto a vacuum source. Twenty-five ml. of test solution was poured over theimmobilized flies, this being sufiicient volume that all flies werecompletely immersed. Vacuum was then applied to remove the testsolution, and the flies were transferred to holding cages lined withabsorbent paper. Mortality counts were made after 24 hours. Results areshown in Table 1. In this and subsequent tables, the amounts of the testingredients are stated in concentration terms of mg. per 100 ml. of testsolution.

TABLE I.SYNERGISTIC COMPOSITIONS OF BUTYL 3- BUTYNYL PHENYLPHOSPHONATESyner- Mortality of gist, housefiies, mg. percent;

50 100 50 38 None 34 Cyclopropanccarboxylate Allethrin 10 None 10(1-cyelohexene-1,2 dicarboximido)methyl chrysanthemumate 50 50 None Theresults in Table I illustrate the synergistic interaction of aphosphonate of this invention with two different syntheticchrysanthemumates.

EXAMPLE 3 The synergistic activity of butyl 3-butynyl phenylphosphonatewith a variety of chrysanthemumate esters was evaluated againsthouseflies by the following procedure: About one microliter of asolution containing the indicated amount of the test materials in 100ml. of acetone was applied topically to each of 35 to 45 threetofourday-old houseflies in one to four replicates. After 24 hours themortality was determined by physical counting of the dead and livingflies, and the percent kill was calculated. Results are shown in Table2.

TABLE 2.-COMPOSITIONS OF BUTYL B-BUTYNYL PHEN- YLPHOSPHONATE ANDCHRYSANTHEMUMATES The results shown in Table 2 are illustrative of thegeneral synergistic interaction between an alkyl w-alkynylphenylphosphonate of this invention and chrysanthemumates. Even atdosages of 72 mg. this phosphonate itself was essentially inactive, yeta consistent and substantial synergistic effect was observed incombinations with chrysanthemumates which themselves produced negligiblekill of houseflies under these test conditions.

EXAMPLE 4 Preparation of propyl 2-propynyl phenylphosphonate Propylphenylphosphinate used in the preparation of this synergist was preparedby the method of Kosolapolf, J.A.C.S. 72, 4292 (1950). Phenylphosphonousdichloride, 126.1 g., was added dropwise with stirring and cooling to127 g. propyl alcohol over a period of minutes. The reaction mixture wasallowed to warm to room temperature. After stirring at room temperaturefor two hours, the reaction mixture was warmed to 40-50 and stirred forone hour. Excess propyl alcohol was removed under reduced pressure (hotwater bath), and the residual oil was vacuum distilled. The major cut,propyl phenylphosphinate, boiled at 103 at 3 mm. Hg 11 1.5140. The totalyield was 88 g. of clear, colorless oil, identified by infrared spectralanalysis.

A solution of 10.8 g. propyl phenylphosphinate in 50 ml. benzene wasadded dropwise to a chilled, stirred solution of 3.7 g. 2-propyn-1-ol,12.8 g. bromotrichloromethane, and 7.1 g. triethylamine in 100 ml.benzene. During this addition the temperature was kept below Whenaddition was complete, the reaction mixture was warmed to roomtemperature, and stirring was continued for 15 hours. Precipitatedtriethylammoninm bromide was removed by filtration and the filtratewashed successively with dilute hydrochloric acid, dilute sodiumhydroxide, and water. The washed organic layer was dried over magnesiumsulfate, and after removal of the drying agent, stripped of solventunder reduced pressure, leaving 13.1 g. of light yellow oil. The productwas distilled (diffusion) with a bath temperature of 109118 at 0.1 1 Hggiving 10.4 g. of propyl 2-propynyl phenylphosphonate as a clear,colorless oil.

Analysis.-Calcd for C H O P (percent): C, 60.50; H, 6.35; P, 13.00.Found (percent): C, 60.52; H, 6.53; P, 13.15.

EXAMPLE 5 The synergistic activity of propyl 2-propynylphenylphosphonate The synergistic insecticidal activity of propyl 2-propynyl phenylphosphonate in combination with allethrin, pyrethrins,and (l-cyclohexene-1,2-dicarboximido)methy1 chrysanthemumate wasdetermined by the test procedure of Example 2. Results are shown inTable 3.

PROPYL 2-PROPYNYL Table 3 shows that propyl 2-propynylphenylphosphonate, itself inactive at the dosage used, is an effectivesynergist for a variety of chrysanthemumates.

EXAMPLE 6 The synergistic activity of propyl 2-propynylphenylphosphonate with a variety of chrysanthemumate esters againsthouseflies was further demonstrated using the test procedure of Example3. Results are shown in Table 4.

TABLE 4.COMPOSITIONS OF PROPYL Z-PROPYNYL PHENYLPHOSPHONATE ANDOHRYSANTHEMUMATES Mortality Synerof gist, houseflies ChrysanthemumateMg. mg. percent Allethrin 14.4 72 71 None 72 4 14.4 None 10 Pyrethrins14.4 72 84 None 72 4 14.4 None 8 (l-cyclohexene-l,2-dicarboximido)methyl14. 4 72 chrysanthemumate None 72 4 14.4 None 7 EXAMPLE 7 Preparation ofsec-butyl 2-propynyl phenylphosphonate The intermediate sec-butylphenylphosphinate was prepared as follows: Under a nitrogen atmosphere25.9 g. phenylphosphonous dichloride was added dropwise with stirring to32.2 g. sec-butyl alcohol. During the 20 minute period of addition thereaction mixture was held at 5-10. The mixture was allowed to warm toroom temperature and was stirred overnight. Excess sec-butyl alcohol wasremoved under reduced pressure to yield 27.8 g. sec-butylphenylphosphinate, identified by infrared spectral analysis.

A solution of 10.0 g. sec-butyl phenylphosphinate in 20 ml. benzene wasadded dropwise to a stirred solution of 3.4 g. 2-propyn-l-ol, 9.4 g.carbon tetrachloride, and 0.2 g. triethylamine in 100 ml. benzene.During addition the reaction mixture was kept at 15-20", then allowed towarm to room temperature and stirred overnight. Precipitatedtriethylammonium chloride was removed by filtration and the filtratewashed successively, twice with 1% hydrochloric acid, once with 0.5%sodium hydroxide, and twice with water. The washed organic layer, driedover magnesium sulfate, was stripped of solvent under reduced pressureand then subjected to high vacuum with vigorous stirring at roomtemperature for six hours. The resulting oil, 8.0 g., identified assec-butyl 2-propynyl phenylphosphonate by infrared spectroscopy, was 98%pure by vapor phase chromatography.

Analysis.Calcd for C H O P (pecent): C, 61.89; H, 6.79; P, 12.28. Found(percent): C, 62.10; H, 6.77; P, 12.31.

EXAMPLE 8 Preparation of isobutyl 2-propynyl phenylphosphonate Followingthe procedure described in Example 7, 25.9 g. phenylphosphonousdichloride was reacted with 32.2 g. isobutyl alcohol to yield 28.7 g.isobutyl phenylphosphinate. The intermediate phosphinate, 10.0 g., wasreacted with 3.4 g. 2-propyn-1-ol, 9.4 g. carbon tetrachloride, and 6.2g. triethyl amine. Vapor phase chromatography showed the product to be98% pure. Distillation in a short path still (diffusion pump, bathtemperature 108-121) gave fractions containing from 97.8 to 99.5% ofisobutyl 2- propynyl phenylphosphonate, identified by infrared spectralanalysis, for a total yield of 8.0 g.

Analysis.-C H O P (percent): C, 61.89; H, 6.79; P, 12.28. Found(percent): C, 61.68; H, 6.71; P, 12.05.

EXAMPLE 9 Preparation of ethyl 4-pentynyl phenylphosphonate Followingthe procedure described in Example 1, 5.85 g. 4-pentyn-1-ol was reactedwith 11.3 g. ethyl phenylphosphonochloridate. The final product, ethyl4-pentyny1 phenylphosphonate, distilled (diffusion system) at a bathtemperature of -130 at 0.01 mm. Hg.

Analysis.-Calcd for C13H17O3P (percent): C, 61.90; H, 6%79; P, 12.28.Found (percent): C, 61.65; H, 7.04; P, 12.1

7 EXAMPLE 10 Preparation of n-butyl 3-butyny1 Z-thienylphosphonateFollowing the procedure described in Example 4, 4.0 g. of 3-butyn-1-olwas reacted with 10.3 g. of n-butyl 2- thienylphosphinate. The product,n-butyl 3-butynyl 2-thienylphosphonate, was distilled in short pathdiffusion apparatus at 0.5 1. Hg with a bath temperature of 128-140. 111.5069.

Analysis.Calcd for C12H170'3PS (percent): C, 52.93; H, 6.29; P, 11.37.Found (percent): C, 53.22; H, 6.46; P, 11.48.

EXAMPLE 11 Preparation of n-octadecyl 3-butyl phenylphosphonateFollowing the procedure of Example 4, 12.6 g. 3- butynylphenylphosphinate was reacted with 17.4 g. noctadecanol. The product,n-octadecyl 3-butynyl phenylphosphonate, recrystallized from hexane, wasa waxy solid, partially molten at room temperature.

Analysis.Calcd for C H O P (percent): C, 72.69; H, 10.24; P, 6.69. Found(percent): C, 72.74; H, 10.33; P, 6.58.

EXAMPLE 12 Preparation of propyl 2-propynyl benzylphosphonate Theintermediate 2-propynyl benzylphosphonochloridate was prepared through aseries of reactions starting with diethyl benzylphosphonate as set forthbelow.

In a flask equipped with heating mantle, stirrer, and reflux condenserwere combined 1000 g. diethyl benzylphosphonate and 3.8 liters of 12 Nhydrochloric acid. After the stirred mixture was heated to 65, enoughdioxane (200-210 ml.) was added to give a clear solution. The solutionwas stirred and refluxed for 64 hours. When the solution was cooled to4550, a solid separated out. The filtered solid was dried in a vacuumoven at 7074 for fifteen hours, giving a yield of 703 g.benzylphosphonic acid, M.P. 171-173".

In a flask equipped with a stirrer, reflux condenser, drying tube, solidaddition funnel, and gas scrubber, a slurry of 111.5 g. benzylphosphonicacid in 1 l. hexane was stirred and warmed to -40". When the first 50 g.portion of a total of 259 g. PCl was added to the mixture, reactionstarted immediately as evidenced by evolution of HCl. The reactionmixture was then cooled to room temperature, and the balance of the PCladded in 50 g. portions over a period of about 2 hours, during whichtime the temperature increased to 60. After the reaction mixture cooledto room temperature, S0 was bubbled through the mixture for fifteenminutes to remove HCl. After removal of solvent under reduced pressure,the product was distilled in a short path still (pressure 0.01 mm., pottemperature 85-125 to give 123.7 g. benzylphosphonic dichloride.

Dipropyl benzylphosphonate was prepared by dropwise addition of 62 g.benzylphosphonic dichloride in 200 ml. benzene to a stirred solution of39.3 g. n-propyl alcohol and 65.9 g. triethylamine in 400 ml. benzene.After stirring overnight the reaction mixture was filtered to removetriethylammonium chloride. The filtered solid was washed with benzene,and the washings added to the filtrate. The clear benzene solution waswashed four times with 100 ml. portions of 1% hydrochloric acid, twicewith 100 ml. portions of 1% sodium hydroxide, and finally with 100 ml.water. The solution was then dried over magnesium sulfate. After removalof solvent under reduced pres sure, the product was distilled in a shortpath still (pressure 0.06 mm., bath temperature 115128) to give a totalyield of 47 g. dipropyl benzylphosphonate, 11, 1.4883, identified byinfrared spectral analysis.

Analysis.Calcd for C H O P (percent): C, 60.93; H, 8.26; P, 12.09. Found(percent): C, 60.97; H, 8.18; P,

Propyl benzylphosphonate was prepared from the intermediate dipropylester as follows: 45 g. dipropyl benzylphosphonate 39 g. sodiumhydroxide, and 350 ml. distilled water were stirred at refluxtemperature for 20 hours, during which period the cloudy reactionmixture became clear. When the pH was adjusted to 1 by dropwise additionof about 125 ml. concentrated hydrochloric acid, a. solid precipitateformed. Since the solid liquified during an attempt at filtration, theproduct was taken into solution by three successive extractions of thereaction mixture with 200 ml. portions of chloroform. After the combinedextracts were dried over magnesium sulfate, solvent was removed underreduced pressure to give a viscous, cloudy liquid. Further subjection tovacuum gave 37.5 g. of sticky, white solid, propyl benzylphosphonate,used in the following synthesis step.

Propyl benzylphosphonochloride was prepared as follows: Under a nitrogenatmosphere, in a flask equipped with a stirrer, gas inlet tube,condenser, and gas scrubber, 37.5 g. propyl benzylphosphonate and 94 g.thionyl chloride were stirred at 4050 for 4 /2 hours. To aid in theremoval of any volatile by-products, two successive ml. portions ofbenzene were added to the reaction mixture at room temperature and thenremoved under reduced pressure. Further subjection to vacuum gave 40.4g. of amber colored liquid, identified by infrared spectroscopy aspropyl benzylphosphonochloridate.

The synergist propyl 2-propynyl benzylphosphonate was prepared asfollows: In a flask equipped with a stirrer, a condenser fitted with adrying tube, and a dropping funnel, 20.5 g. propylbenzylphosphonochloridate in 50 ml. benzene was added dropwise, over aperiod of 30 minutes, to a stirred solution of 5.5 g. 2-propyn-1-ol and9.8 g. triethylamine in 100 ml. benzene. After stirring at roomtemperature for about 15 hours, the solution was filtered free oftriethylammonium chloride, and washed twice with 50 ml. 1% sodiumhydroxide and once each with 50 ml. 1% hydrochloric acid and 50 ml.water. The solution was dried over magnesium sulfate and the solventremoved under reduced pressure to give an amber colored oil. The crudeproduct was distilled in a molecular still (0.0001- 0.00015 mm. Hg, bathtemperature C.) to give 14.5 g. propyl 2-propynyl benzylphosphonate, alemon colored oil, n 1.5074.

Analysis.Calcd for C13H17O3P (percent): C, 61.90; H, 6.79; P, 12.28.Found (percent): C, 61.81; H, 6.80; P, 12.16.

EXAMPLE 13 Preparation of propyl 3-butynyl benzylphosphonate Preparationof ethyl Z-propynyl benzylphosphonate The procedure of Example 12 wasused to prepare ethyl 2-propynyl benzylphosphonate, identified byinfrared spectral analysis, 11 1.5124.

Analysis.-Calcd for C H O P (percent): C, 60.50; H, 6.35; P, 13.00.Found (percent): C, 60.56; H, 6.45; P, 12.73.

EXAMPLE 15 Preparation of ethyl 2-propynyl 4-chlorobenzylphosphonate Theprocedure of Example 12 was followed except that in the present examplethe unsaturated alcohol was reacted with the phosphonate moiete first,and the saturated alcohol was reacted second. Thus4-chlorobenzylphosphonic dichloride was converted to di-2-propynyl4-chlorobenzylphosphonate, and in the last step 2-propynyl4-chlorobenzylphosphonochloridate was reacted with ethyl a1- cohol togive ethyl 2-propynyl 4-chlorobenzylphosphonate, identified by infraredspectral analysis, n, 1.5218.

Analysis.--Calcd for C H ClO P (percent) C, 52.86; H, 5.18; P, 11.36.Found (percent): C, 53.14; H, 5.36; P, 11.15.

EXAMPLE 16 Preparation of propyl 2-propynyl 4-chlorobenzylphosphonateFollowing the procedure of Example 15, 2-propynyl 4-chlorobenzylphosphonochloridate was reacted with npropyl alcohol to givepropyl 2-propynyl 4-chlorobenzylphosphonate, identified by infraredspectral analysis, 11 1.5174.

Analysis.-Calcd for C H clO P (percent): C, 54.46; H, 5.63; P, 10.80.Found (percent): C, 53.72; H, 5.81; P, 11.14.

10 EXAMPLE 17 Preparation of propyl 2-propynyl3,4-dichlorobenzylphosphonate Following the general proceduresexemplified above, a large number of compounds of this class are readilysynthesized. The synergistic activity of typical phosphonates of thisinvention, in combination with typical and useful insecticidalcyclopropanecarboxylates is further illustrated in Table 5. Theseresults were obtained following the procedure described in Example 2.

TABLE 5.-SYNERGISTIC TNSEOTICIDAL COMPOSITIONS Mortality of houseflies,Cyelopropanecarboxylate Mg. Phosphonate Mg percent(l-cyelohexene-l,2-diearboxirnido)methyl chrysanthemumate N 10 Methyl2-propynyl phenylphosphonate 108 one 50 10 None 11 Pyr 10 Methyl3-butynyl phenylphosphonate 50 100 None 50 20 10 None 3 AllethrnL- 10Ethyl 3-butynyl phenylphosphonate 50 1 None 50 36 10 None 8 10 Ethyl4-pentyny1 phenylphosphonate 50 79 None 50 0 10 None 8 Pyre 10 Ethyl3-butyny1 benzylphosphonate 50 10 None 50 7 10 None 3 10 Ethyl4-pentynyl benzylphosphonate 50 10 None 50 38 10 None 3 Allethrm- 10Ethyl 3-butynyl 4-fluorobenzylphosphonate 50 10 None 50 8 10 None 8(l-cyclohexene-l,Z-dicarboxlmido) methyl chrysanthemumate- N 10 n-PropylB-butynyl phenylphosphonate 50 19 one 50 10 None 12 Pyr 10 n-Propyl4pentyny1 phenylphosphonate 50 10 None 50 3 10 None 3 Allethrin- 10i-Propyl Z-propynyl phenylphosphonate 50 10 None 50 0 10 None 33(l-eyclohexene-l,2-d1carboxim1do)methyl chrysanthemumate N 10 2-propeny12flpropynyl phenylphosphonate 5g 1 3 one 5 10 None 11 Pyr 10 Z-propenyl3-butyny1 phenylphosphonate 50 5 None 50 0 10 None 7(LeyclohexenB-l,%dicarbox1m1do)methyl chrysanthemumate N 10 n-Butyl3-butynyl 2-thienylphosphonate 50 138 one 50 10 None 24 10 n-Ientyl2-propyny1 phenylphosphonate 100 None 19 10 None 28 Allethrm- 10n-Pentyl 3-butyny1 phenylphosphonate 10 None 50 0 10 None 39(l-eyclohexene-l,2-d1carbox1mido)methyl chrysanthemumate N 10 n-Pentyl4-pentyny1 phenylphosphonate 50 108 one 50 10 None 28 Allethrrn 10n-Dodecyl 3-butynyl phenylphosphonate 50 84 None 50 3 10 None 33 10b-Oetadecyl 3-butynyl phenylphosphonate 50 93 None 50 10 10 None 19 PyrN 10 sec-Butyl 2propynyl phenylphosphonate 103 one 10 None 31 10Isobutyl 2-propynyl phenylphosphonate 50 None 50 0 10 None 31 Allethrin10 n-Propyl 2-propynyl benzylphosphonate 50 100 None 50 4 10 None 7Pyrethrms 10 n-Propyl 3-butyny1 benzylphosphonate 50 100 None 50 3 None21 TABLE 5Continued Mortality of htiiuseres Cyclopropanecarboxylate Mg.Phosphonate Mg. percent (l-eyelohexene-l,2-dicarboximido)methylchrysanthemmnate.. N '10 Ethyl Z-propynylbenzylphosphonate 50 103 one 505 4 10 None 30 Allethrin l Ethyl 2-propynyl 4-chlorobenzylphosphonate 50100 None 50 0 10 None 3 Pyrethrms 10n-Propyl2-propynyl4-011lorobenzylphosphonate 50 100 None 50 3 I 10 None11 (l-cyclohexene-l,2-dicarbox1m1do)methyl chrysanthcmumate N 10n-Propyl2propynyl 3,4-dichlorobenzylphosphonate. 50 100 one 50 10 None35 EXAMPLE 44 The synergistic activity of the phosphonates of thisinvention with chrysanthemumates over a wide range of chrysanthemumateto synergist ratios was demonstrated by a series of tests carried out bythe method described in Example 2. Results for two differentchrysanthemumatesynergist combinations are shown in Table 6.

TABLE 6,-COMPOSITIONS WITH DIFFERENT CHRYSANTHEMUMATE TO SYNERGISTRATIOS Mortality of houseflies, percent Mg. ehrysanthemumato Mg. syner-Ratio, Compo- Compo- (A) gist (B) AzB sition I sition II None 9 13 5 1:283 61 5 25 1:5 100 78 5 50 1: 10 100 97 5 100 1:20 100 100 5 250 1:50100 100 None 100 8 23 None 250 3 41 Composition I.Chrysanthemumate=(l-cyclohexene-l,2-dicarboximido)methyl chrysanthemumate;Synergist=propyl 2-propynyl phenylphosphonate.

Composition IL-Chrysanthemumate=Allethrin; Synergist=Butyl 3- butynylphenylphosphonate.

The results in Table 6 illustrate the marked synergistic interactionfound over a wide range of ratios.

EXAMPLE 45 Synergistic activity over a wide range ofcyclopropanecarboxylate to synergist ratios was further demonstrated bya series of tests of representative phosphonates of the invention with(5-benzyl-3-furyl)methyl 2,2,3,3-tetramethylcyclopropanecarboxylate. Thetest method was as described in Example 2, but with lower concentrationsowing to the high level of activity of the cyclopropanecarboxylate.Results are shown in Table 7.

TABLE 7.(5-BENZYL-3-FURYL)METHYL 2,2,3,3-TETRA-METHYLCYOLOPROPANECARBOXYLATE IN SYNER- GISTIC COMPOSITIONS Mg.Mortality of houseflies Mg. oyolopropanecarboxylate synergist (B) A onlyB only A+B Synerglst L-Propyl 2-propynyl phenylphosphonate. SynergistII.Isobutyl Z-propynyl phenylphosphonate. Synergist IIL-Propyl 3-butynylbenzylphosphonate.

EXAMPLE 46 The effectiveness of the synergistic compositions of thisinvention is strikingly shown in aerosol formulations, as illustrated inthe following example: Aerosol formulations were prepared containing atypical insecticidal chrysanthemumate, both with and without thesynergist, in this example butyl 3-butynyl phenylphosphonate, asfollows:

With Without synergist, g. synergist, g.

(l-cycl0hexene-l,2-dicarb0ximid0)-methy1 chrysauthemumate active) 0. 0.140 Butyl 3-butynyl phenylphosphonate 0. 625 None Heavy aromaticnaphtha. 6. 00 6. 00 Purified kerosene 3. 24 3. 86Triohloromonofluoromethan 20. 00 20. 00 Dichlorodifluoromethane 20. 0020. 00

A group of 200 to 300 houseflies was introduced into a 216 cu. ft. testchamber, prepared according to the specifications of the ChemicalSpecialties Manufacturers Association (Soap and Chemical Specialties,1961 Blue Book, p. 244). Measured amounts of the aerosol formulationswere introduced into the chamber. Results, shown in Table 8, are theaverages of nine replicates for the composition containing the synergistand of two replicates for the composition containing thechrysanthemumate alone.

TAB LE 8.AE ROSOL F0 RMULATIONS Percent Average dose Knockdown MortalityComposition (g./1,000 itfi), g. 15 minutes 24hours With synergist 3.1584 71 Without synergist... 2. 92 85 14 It is of particular interest tonote that butyl 3-butynyl phenylphosphonate enhanced to a marked extentthe percent kill obtained with this chrysanthemumate, which by itselfexhibited excellent knockdown of houseflies, but very poor permanenteffectiveness.

In addition to the specific phosphonates exemplified herein, similarsynergistic behavior characterizes the other members of the classdescribed, including but not limited to the following:

13 i-amyl 3-butynyl(2-pyridyl)phosphonate; 2-methoxyethyl 2-propynylphenylphosphonothionate; n-hexyll-ethyl-2-propynyl(4-chlorobenzyl)phosphonate;

and the like.

The novel synergists of this invention may be prepared by adaptation ofthe synthetic procedures illustrated above, i.e. from suitablephosphonochloridates or phosphinates as well as by other knownprocedures. These procedures are well described in the chemicalliterature, for example by Kosalopoff, J.A.C.S. 72, 4292 (1950); Hudsonet al., J. Chem. Soc., 1859 (1960); Harman et al., U.S. P-at. 2,659,714;Bentov et al., J. Chem. Soc., 4750 (1964); and Cherbuliez et al., Helv.Chirn. Acta, 46, 2464 (1963).

The novel synergists described herein have a degree of effectiveness notshared by certain closely related compounds. The nature and location ofthe unsaturated linkage has been found to have a marked elfect on thesynergistic effectiveness of this class of compounds. For example,reduction of the acetylenic linkage to an olefinc or a saturated linkagediminishes the synergistic activity. Displacement of the acetyleniclinkage from the terminal position also decreases the activity.

The synergistic compositions of this invention may be employed tocontrol a variety of crop pests and household pests. These compositionsare not usually applied full strength, but are generally incorporatedwith the adjuvants and carriers normally employed for facilitatingdispersion of active ingredients for insecticidal applications(recognizing the accepted fact that the formulation and mode ofapplication may affect the activity of a material. Striking results areobtained when these compositions are applied as space sprays and aerosolsprays, for example, or are formulated into any of the diluted andextended types of formulations used in insecticidal practice, includingdusts, wettable powders, emulsifiable concentrates, solutions,granulars, baits, and the like, for application to foliage, Withinenclosed areas, to surfaces, and wherever insect control is desired.

These synergistic compositions may be made into liquid concentrates bysolution or emulsification in suitable liquids, and into solidconcentrates by admixing the active components with talc, clays, andother solid carriers used in the insecticide art. Such concentratesnormally contain about 5-80% of the toxic composition, and the restinert material which includes dispersing agents, emulsifying agents, andwetting agents. For practical application, the concentrates are normallydiluted with water or other liquid for liquid sprays, with liquefiedpropellants for aerosols, or with additional solid carrier forapplications as a dust or granular formulation. Baits are usuallyprepared by mixing such concentrates with a suitable insect food, suchas mixtures of cornmeal and sugar, and insect attractants may also bepresent. The concentration of the active ingredients in the dilutedformulations, as generally applied for control of insects, is normallyin the range of about 0.001% to about 5%. Many variations of sprayingand dusting compositions are well known in the art, as are thetechniques for formulating and applying these compositions.

Employing the synergistic pesticidal compositions described herein,enhanced control is obtained of both crop and household pests, includinginsects and acarids against which the cyclopropanecarboxylates arethemselves effective, but at higher concentrations. This includes flyingand crawling pests of the orders Coleoptera (beetles), Hemiptera (truebugs), Homopter-a (aphids), Diptera (flies), Orthoptera (roaches),Acarina (mites and ticks), and Lepidoptera (butterflies and mothsincluding their larvae). Because of the low mammalian toxicity of thesecompositions, they are preferred to compositions for use in control ofpests in an environment inhabited by man and animals, including controlof flies, mosquitoes, ants, roaches, moths, ticks, and the like, as wellas in uses such as packaging, food and grain protection, and garden,pet, and livestock uses.

The relative amounts of synergist and chrysanthemumate employed are notcritical, in that a relatively minor amount, e.g., less than one part ofsynergist per part of chrysanthemumate, is effective in imparting abeneficial effect to the combination. From practical considerations, itis preferred to use larger amounts of synergist, for example, from twoto fifty parts of synergist per part of cyclopropanecarboxylate. Evenlarger proportions of synergist may be employed Without detriment,whether or not the optimum synergistic proportions have been achieved.It is clear that effective amounts of synergist should be employed inthe compositions, that the components should be present in synergisticproportions, and that effective amounts of the compositions, to controlthe particular insect pests in the environment of infestation, should beapplied.

It is apparent that many modifications may be made in the formulationand application of the compositions of this invention, without departingfrom the spirit and scope of the invention, and of the following claims.

We claim:

1. A compound of the formula OR CECH References Cited UNITED STATESPATENTS 5/1951 Ladel 260956 X JOSEPH P. BRUST, Primary Examiner A. H.SUTTO, Assistant Examiner US. Cl. X.R.

